CN116854880A - 一种开孔聚氨酯硬质泡沫及其制备方法 - Google Patents
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Abstract
本发明涉及聚氨酯材料技术领域,提出了一种开孔聚氨酯硬质泡沫及其制备方法,所述原料包括以下重量份组分:100份多元醇、0.5‑5份催化剂、0.5‑4份水、5‑40份发泡剂、0.5‑3份表面活性剂、0.5‑3份开孔剂、150‑160份异氰酸酯;所述多元醇包括低羟值聚醚多元醇和高官能度聚醚多元醇;所述低羟值聚醚多元醇的羟值≤56mg/gKOH。通过上述技术方案,解决了现有技术中因初期骨架强度高,导致聚氨酯硬质泡沫开孔率低的问题。
Description
技术领域
本发明涉及聚氨酯材料技术领域,具体的,涉及一种开孔聚氨酯硬质泡沫及其制备方法。
背景技术
聚氨酯硬质泡沫一般为闭孔结构,强度高、重量轻、具有极佳的保温性能,在冰箱冰柜、太阳能、冷库、管道保温等领域应用广泛。但是,当聚氨酯硬泡应用在海上油气管道补口部位时,需要改变聚氨酯硬泡转变为开孔结构。
目前,在制备聚氨酯硬质泡沫时通常加入开孔剂或者开孔硅油来实现聚氨酯硬质泡沫的开孔。但聚氨酯硬泡通常使用高官能度的聚醚,高官能度的聚醚刚性强,官能度高、羟基含量大,造成聚氨酯在发泡初期就形成了较高的泡沫强度,发泡气体的膨胀不足以冲破气泡壁,在发泡过程中很容易形成闭孔结构,虽然使用了开孔剂,但不能从根本上降低发泡体在发泡初期骨架的强度,因此很难获得高开孔率的聚氨酯硬质泡沫。
发明内容
本发明提出一种开孔聚氨酯硬质泡沫及其制备方法,解决了相关技术中因初期骨架强度高,导致聚氨酯硬质泡沫开孔率低的问题。
本发明的技术方案如下:
一种开孔聚氨酯硬质泡沫,原料包括以下重量份组分:100份多元醇、0.5-5份催化剂、0.5-4份水、5-40份发泡剂、0.5-3份表面活性剂、0.5-3份开孔剂、150-160份异氰酸酯;所述多元醇包括低羟值聚醚多元醇和高官能度聚醚多元醇;所述低羟值聚醚多元醇的羟值≤56mg/gKOH。
作为进一步技术方案,所述低羟值聚醚多元醇的羟值为50-56mg/gKOH。
作为进一步技术方案,所述多元醇由以下重量百分比组成:5-30%低羟值聚醚多元醇、70-95%高官能度聚醚多元醇。
作为进一步技术方案,所述低羟值聚醚多元醇的官能度为,2≤官能度≤3。
作为进一步技术方案,所述高官能度聚醚多元醇的羟值≥300mg/gKOH;官能度≥4。
作为进一步技术方案,所述高官能度聚醚多元醇的羟值为450-500mg/gKOH。
作为进一步技术方案,所述催化剂包括N,N-二甲基环己胺、N,N-二甲基苄胺、三亚乙基二胺、三乙醇胺、二甲基乙醇胺、三乙胺、双(2-甲氨基)乙醚、二月桂酸二正丁基锡、辛酸亚锡、异辛酸铋、异辛酸铅、环烷酸铅、钛酸四丁酯和钛酸四异丙基酯中的一种或多种。
作为进一步技术方案,所述物理发泡剂包括正戊烷、环戊烷、异戊烷、一氟二氯乙烷、五氟丙烷和反式-1,3,3,3-四氟丙烯中的一种或多种。
作为进一步技术方案,所述表面活性剂为硅油。
本发明还包括一种开孔聚氨酯硬质泡沫的制备方法,包括以下步骤:
S1、称取所述的原料,备用;
S2、将多元醇、催化剂、水、发泡剂、表面活性剂、开孔剂混合后,得到混合物;
S3、向混合物中加入异氰酸酯混合进行发泡,制得开孔聚氨酯硬质泡沫。
本发明的工作原理及有益效果为:
1、本发明将低羟基的聚醚多元醇引入到聚氨酯硬质泡沫中,降低了泡沫体在发泡初期的强度,使得发泡时气体膨胀冲破气泡壁,自然形成开孔结构,显著提高了开孔率,并且得到的聚氨酯硬质泡沫仍具有较高的强度。
2、本发明中通过限定多元醇中低羟值聚醚多元醇和高官能度聚醚多元醇的质量比,能够进一步提高聚氨酯硬质泡沫的开孔率和抗压强度。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都涉及本发明保护的范围。
下述实施例及对比例中,220聚醚、330N聚醚、8345聚醚均购自山东一诺威新材料有限公司;N,N-二甲基环己胺、N,N-二甲基苄胺、三亚乙基二胺和发泡剂245fa均采购自上海鑫锐化工科技有限公司;硅油8803和开孔剂M-9901均购自江苏美斯德公司;PM200聚合MDI购自烟台万华;聚醚2045,羟值为29,购自宁波宏义化工有限公司;聚醚多元醇IV6630,羟值为550,购自济宁华凯树脂有限公司。
实施例1
S1、将20份220聚醚、80份聚醚多元醇8345、0.3份N,N-二甲基环己胺、1.2份N,N-二甲基苄胺、0.6份三亚乙基二胺、1.5份水、30份发泡剂245fa、2份硅油8803、1份开孔剂混合后,得到混合物;其中220聚醚的羟值为56,官能度为2,聚醚多元醇8345的官能度5.5,羟值为450;
S2、将混合物与150份PM200聚合MDI混合后,通过高压机枪头进行混合发泡,制得开孔聚氨酯硬质泡沫;其中枪头的压力为10MPa。
实施例2
S1、将30份220聚醚、70份聚醚多元醇8345、0.3份N,N-二甲基环己胺、1.2份N,N-二甲基苄胺、0.6份三亚乙基二胺、1.5份水、30份发泡剂245fa、2份硅油8803、1份开孔剂混合后,得到混合物;其中220聚醚的羟值为56,官能度为2,聚醚多元醇8345的官能度5.5,羟值为450;
S2、将混合物与150份PM200聚合MDI混合后,通过高压机枪头进行混合发泡,制得开孔聚氨酯硬质泡沫;其中枪头的压力为10MPa。
实施例3
S1、将15份330N聚醚、85份聚醚多元醇8345、0.3份N,N-二甲基环己胺、1.2份N,N-二甲基苄胺、0.6份三亚乙基二胺、1.5份水、30份发泡剂245fa、2份硅油8803、1份开孔剂混合后,得到混合物;其中330N聚醚的羟值为33,官能度为3;聚醚多元醇8345的官能度5.5,羟值为450;
S2、将混合物与150份PM200聚合MDI混合后,通过高压机枪头进行混合发泡,制得开孔聚氨酯硬质泡沫;其中枪头的压力为10MPa。
实施例4
S1、将5份330N聚醚、95份聚醚多元醇8345、0.3份N,N-二甲基环己胺、1.2份N,N-二甲基苄胺、0.6份三亚乙基二胺、1.5份水、30份发泡剂245fa、2份硅油8803、1份开孔剂混合后,得到混合物;其中330N聚醚的羟值为33,官能度为3;聚醚多元醇8345的官能度5.5,羟值为450;
S2、将混合物与150份PM200聚合MDI混合后,通过高压机枪头进行混合发泡,制得开孔聚氨酯硬质泡沫;其中枪头的压力为10MPa。
实施例5
S1、将5份220聚醚、95份聚醚多元醇8345、0.5份N,N-二甲基环己胺、0.5份水、5份发泡剂245fa、0.5份硅油8803、0.5份开孔剂混合后,得到混合物;其中220聚醚的羟值为56,官能度为2,聚醚多元醇8345的官能度5.5,羟值为450;
S2、将混合物与160份PM200聚合MDI混合后,通过高压机枪头进行混合发泡,制得开孔聚氨酯硬质泡沫;其中枪头的压力为10MPa。
实施例6
S1、将30份220聚醚、70份聚醚多元醇8345、5份N,N-二甲基环己胺、4份水、40份发泡剂245fa、3份硅油8803、3份开孔剂混合后,得到混合物;其中220聚醚的羟值为56,官能度为2,聚醚多元醇8345的官能度5.5,羟值为450;
S2、将混合物与160份PM200聚合MDI混合后,通过高压机枪头进行混合发泡,制得开孔聚氨酯硬质泡沫;其中枪头的压力为10MPa。
实施例7
与实施例1相比,实施例7的不同之处在于220 聚醚5份,聚醚多元醇8345 95份。
实施例8
与实施例1相比,实施例8将220聚醚替换为等量的聚醚2045,其他与实施例1相同。
实施例9
与实施例1相比,实施例9将聚醚多元醇8345替换为等量的聚醚多元醇IV6630,其他与实施例1相同。
对比例1
S1、将100份聚醚多元醇8345、0.3份N,N-二甲基环己胺、1.2份N,N-二甲基苄胺、0.6份三亚乙基二胺、1.5份水、30份发泡剂245fa、2份硅油8803、1份开孔剂混合后,得到混合物;其中聚醚多元醇8345的官能度为5.5,羟值为450;
S2、向混合物中加入150份PM200聚合MDI进行发泡,得到开孔聚氨酯硬质泡沫。
试验例
按照GB/T 20219-2015《绝热用喷涂硬质聚氨酯泡沫塑料》中的方法测定实施例1-9及对比例1制备得到的聚氨酯硬质泡沫的自由泡密度、抗压强度和开孔率,测定结果如表1所示。
表1实施例1-9及对比例1聚氨酯硬质泡沫的性能测定结果
与实施例1相比,对比例1没有添加220聚醚,结果对比例1制备得到聚氨酯硬质泡沫的抗压强度与实施例1基本相同,开孔率远低于实施例1。说明本发明通过引入羟值为50-56mg/gKOH的低羟值聚醚多元醇,可以显著提高聚氨酯硬质泡沫的开孔率,并且具有较高的抗压强度。
与实施例1相比,实施例8中将220聚醚替换为等量的聚醚2045,实施例9将聚醚多元醇8345替换为等量的聚醚多元醇IV6630,结果实施例8制备得到的聚氨酯硬质泡沫的抗压强度低于实施例1,实施例9制备得到的聚氨酯硬质泡沫的开孔率低于实施例1。说明本发明中通过限定多元醇中低羟值聚醚多元醇的羟值为50-56mg/gKOH和高官能度聚醚多元醇的羟值为450-500mg/gKOH,可以更进一步的同时提高聚氨酯硬质泡沫的开孔率和抗压强度。
与实施例1、实施例7相比,实施例2制备得到的聚氨酯硬质泡沫的抗压强度和开孔率均高于实施例1和实施例7。说明当低羟值聚醚多元醇为多元醇质量的30%,高官能度聚醚多元醇为多元醇质量的70%时,制备得到的聚氨酯硬质泡沫抗压强度和开孔率较高。
以上仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种开孔聚氨酯硬质泡沫,其特征在于,原料包括以下重量份组分:100份多元醇、0.5-5份催化剂、0.5-4份水、5-40份发泡剂、0.5-3份表面活性剂、0.5-3份开孔剂、150-160份异氰酸酯;所述多元醇包括低羟值聚醚多元醇和高官能度聚醚多元醇;所述低羟值聚醚多元醇的羟值≤56mg/gKOH。
2.根据权利要求1所述的一种开孔聚氨酯硬质泡沫,其特征在于,所述低羟值聚醚多元醇的羟值为50-56mg/gKOH。
3.根据权利要求1所述的一种开孔聚氨酯硬质泡沫,其特征在于,所述多元醇由以下重量百分比组成:5-30%低羟值聚醚多元醇、70-95%高官能度聚醚多元醇。
4.根据权利要求1所述的一种开孔聚氨酯硬质泡沫,其特征在于,所述低羟值聚醚多元醇的官能度为,2≤官能度≤3。
5.根据权利要求1所述的一种开孔聚氨酯硬质泡沫,其特征在于,所述高官能度聚醚多元醇的羟值≥300mg/gKOH;官能度≥4。
6.根据权利要求1所述的一种开孔聚氨酯硬质泡沫,其特征在于,所述高官能度聚醚多元醇的羟值为450-500mg/gKOH。
7.根据权利要求1所述的一种开孔聚氨酯硬质泡沫,其特征在于,所述催化剂包括N,N-二甲基环己胺、N,N-二甲基苄胺、三亚乙基二胺、三乙醇胺、二甲基乙醇胺、三乙胺、双(2-甲氨基)乙醚、二月桂酸二正丁基锡、辛酸亚锡、异辛酸铋、异辛酸铅、环烷酸铅、钛酸四丁酯和钛酸四异丙基酯中的一种或多种。
8.根据权利要求1所述的一种开孔聚氨酯硬质泡沫,其特征在于,所述物理发泡剂包括正戊烷、环戊烷、异戊烷、一氟二氯乙烷、五氟丙烷和反式-1,3,3,3-四氟丙烯中的一种或多种。
9.根据权利要求1所述的一种开孔聚氨酯硬质泡沫,其特征在于,所述表面活性剂为硅油。
10.根据权利要求1所述的一种开孔聚氨酯硬质泡沫的制备方法,其特征在于,包括以下步骤:
S1、称取如权利要求1所述的原料,备用;
S2、将多元醇、催化剂、水、发泡剂、表面活性剂、开孔剂混合后,得到混合物;
S3、向混合物中加入异氰酸酯混合进行发泡,制得开孔聚氨酯硬质泡沫。
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